Paraffin wax compositions



2,694,014 PARAFFIN WAX COMPOSITIONS Robert G. Capell, William P. Ridenour, and John A. Stewart, Pittsburgh, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporah'on of Delaware No Drawing. Application May 16, 1950, Serial No. 162,389

4 Claims. (Cl. 106270) This invention relates to improved parafiin wax compositions, and more particularly to paraffin wax compositions stabilized against oxidative and analogous forms of deterioration resulting from subjecting paraffin wax to elevated temperature, air, and the like.

The methods of separating paraflin wax from crude petroleum products, such as by distillation, chilling with filtering or centrifuging, sweating, and solvent extraction, are well known. Various methods of paraffin wax purification, such as treatment with sulfuric acid and fullers earth are also well known. Although this purification helps to produce more stable paratfin waxes, initially free from odor, taste, and color, it is not effective enough to prevent subsequent oxidative deterioration which has been troublesome to industrial users of parafiin wax.

One of the most widely practiced applications of paraffin wax is in the coating industry wherein hot wax baths are employed for waterproofing, treating, impregnating or sizing paper and similar products, and wherein wax is employed to provide a protective coating for materials of all kinds. More specifically, the use of hot liquefied wax is widely practiced in the manufacture of such articles as waxed paper, especially waxed bread wrappers,

waxed milk cartons and other beverage containers, car

tons, bottle caps, shot shell tubes, matches, wax impregnated fabrics, paper-metal foil electrical condensers, junction and terminal boxes, transformers, wax impregnated insulation, coils and windings, candles, as well as a host of other products too numerous to mention.

In each instance wherein a hot bath of liquefied paraffin wax is employed, problems of wax decomposition must be dealt with. This decomposition, which is generally considered to be the result of an oxidative mechanism, is evidenced by the appearance of undesirablei'odors, discoloration of the wax, and the formation of organic acids, peroxides, and possibly anhydrides and'lactones in the wax. Thus, suppliers of refined paraffin wax generally recommend that the temperature of a wax melt be kept below 160 F. (71 C.) because, beginning at about this temperature, decomposition starts, accompanied by the development of an acroleinic or burnt odor, a similar taste and a darkening of the color. Parafiin waxes ranging in melting point from 59 F. C.) to 176 having from fifteen to thirty-five straight chain carbon atoms are readily oxidized in contact with air above 160 F. By way of example, after 50 hours at 200 F. a parafiin wax having a melting point of 122 F. begins to show traces of peroxides, and after 90 hours at 212 F a titratable amount of fatty acid has developed.

Besides the formation of objectionable odors and an increase in color and acidity, oxidation brings about a lowering of melting point and tensile strength, and an overall deterioration of valuable properties such as hardness and the like, of the wax. Moreover, when decomposition occurs, much wax is lost through volatilization and the periodic purification steps necessitated by this decomposition. Consequently, it is of considerable importance to improve the heat stability of parafiin wax.

Wax compositions of improved heat stability, moreover, offer many processing advantages. Wax coating and impregnating baths may be operated safely at higher temperatures to effect improved penetration, while allowing better control over the amount of wax pick-up by the paper or other stock being treated. In addition, entirely new applications, previously eliminated from consideration because of temperature limitations, become practicable for waxes having improved heat-stability. For- United States Patent 0 thermore, tank cars may be unloaded more rapidly because higher temperatures resulting in lower viscosities give better transfer of heat and flow, making possible savings in labor and steam costs.

A further problem encountered by users of paraifin wax is that of providing a finished product, such as Waxed paper and beverage containers, which will not deteriorate or discolor upon exposure to air. The salability of food products in wrappings and containers impregnated with wax is adversely affected by discoloration or yellowing of the wax due to oxidation. This ditficulty becomes more acute with the recent emphasis placed on packaging and package design.

It has been proposed to improve the stability of parafiin waxes against oxidative deterioration by incorporating therewith one or more materials called anti-oxidants because such materials are believed to inhibit the formation of undesirable products of oxidation. However, the inhibition of parafiin wax against oxidation presents special difficulties not encountered when choosing an anti-oxidant for other purposes. First, the anti-oxidant material must be capable of withstanding the temperatures employed in wax melts without loss in anti-oxidant powers. This problem, and oxidation conditions in general, are accentuated in the blending of paraifin wax with higher melting point materials such as polyethylene, as set forth in copending application Ser. No. 601,556, filed June 25, 1945, by Bowman, Ridenour and Hollenback and assigned to the same assignee as the present application. The higher temperatures and agitation employed tend to increase oxidation. Accordingly, anti-oxidants which are suitable in mild temperature applications may not be suitable in paraflin Wax. In addition, an anti-oxidant must not adversely affect the physical properties of the wax.

Where paraffin wax is employed in the manufacture of wrappings, containers, and coatings for foods, an anti-oxidant must not impart color, odor, or taste to the wax, either in the wax melt or when in contact with the food. The standards for paraifin wax are generally much higher than for most other products including many edible products such as edible fats and oils. This is particularly true with regard to color and odor. Lard oil, for example, has a characteristic odor which although not objectionable from a standpoint of human consumption would be highly objectionable if found in paraffin wax compositions. Any color imparted to paraffin wax is highly objectionable from a marketing standpoint and, therefore, a very small degree of oxidation which might give only a slight oif-white cast to the wax is undesirable, whereas in petroleum oils in general and in many food products a slight discoloration goes unnoticed. Paraflin wax is essentially odorless and, therefore, any odor due to impurity is very easily detected. For example, oxidation of paraffin wax to such a degree that it has a peroxide number of 0.01 is usually enough to confer a definitely detectable oxidized odor. Such a small amount of oxidation with its attendant odor may go unnoticed in many other substances which have some slight characteristic odor of their own, the characteristic odor tending to mask the oxidized odor. Since paraffin wax is a crystalline material, small amounts of impurities can effect relatively large changes in physical properties such as melting point and tensile strength. Small amounts of impurities in nicfm-crystalline substances will not exert such a noticeable e ect.

The essentially completely odorless and tasteless character of parafiin wax combined with the fact that the oxidation of parafiinic-type compounds always leads to soluble oxidation products which tend to affect taste and odor makes the problem of inhibiting parafiin wax one that is both difiicult and unique. The rigid requirements in the trade for parafiin wax are therefore such that an anti-oxidant for parafiin wax must be efiective in very low concentrations where it will not cause taste or odor by itself, and at the same time it must, in that low concentration, be so effective that the formation of even extremely small amounts of odorand taste-producing, d'ecomposition products is suppressed.

The question of whether or not any material will satisfactorily function as an anti-oxidant in any medium is quite unpredictable, for anti-oxidant action is highly selective and apparently catalytic. It is so selective, in fact, that one cannot predict with any degree of certainty that a material which is a known anti-oxidant for one substance will still perform as a satisfactory anti-oxidant in another medium. For example, it is well known that many phenolic materials are useful as anti-oxidants for various purposes, but a wide variety of these phenolic materials are not suitable as wax anti-oxidants. To illustrate, a number of phenolic compounds, known to possess antioxidant properties in other environments, have been tested in parafiin wax and found to be unsatisfactory as parafiin wax anti-oxidants. These compounds are as follows: his (4-hydroxyphenyl) isopropane; bis (4-hydroxyphenyl) cyclohexane; orthodihydroxybenzene; metadihydroxybenzene; bis (Z-methoxyphenyl) methane; 2,5-ditertiarybutyl hydroquinone; 3-pentadecylphenol; bis (2-hydroxy-3,5,-ditertiarybutyl-6-methyl phenyl) methane; 1,1,2,2,-tetrakis (2 methyl 4 hydroxy tertiarybutylphenyl) ethane. Thus, a material which may be found to exhibit antioxidant properties in fats and oils cannot on that basis be expected to exhibit anti-oxidant properties in paraflin wax. Furthermore, it is difficult to predict that such a material would be otherwise suitable for use in wax compositions. Apparently, the nature of paraffin wax has considerable bearing on the question.

It is therefore an object of our invention to provide new paraflin wax compositions having improved stability against general decomposition or oxidative deterioration.

More specifically, a further object of our invention is to provide new paraffin wax compositions of improved heat stability, such as stability against decomposition in the hot liquefied state.

A still further object of our invention is to provide new paraffin wax compositions having stability against deterioration due to the action of air.

Another object of our invention is to provide improved paraflin wax compositions having good color and exhibiting substantially no odor or taste, such that they may be employed in food packaging.

These and other objects are accomplished by the present invention wherein we provide improved paraffin wax compositions comprising a major amount of a refined paraffin wax and a minor amount, sufficient to inhibit oxidative deterioration, of conidendrol having the following structural formula:

0%: /O CHO l l 0 E0 ctr-43hr Conidendrol exists in two isomeric forms, both of which have the structural formula shown above. These are known as the alpha and beta forms. Alpha-comdendrol and beta-conidenrol are by-products of the pulp and paper industry. They are produced from conidendrin, which differs structurally from the conidendrols only in the presence of two methoxy groups, each on one of the benzene rings. Conidendrin has been isolated from a variety of coniferous woods, the most prevalent source material being western hemlock. Thus far, one of the most convenient means for obtaining conidendrin has been by solvent extraction from the sulfite waste liquors produced during the pulping of western hemlock. The conidendrols may then be prepared by demethylation of conidendrin through methods well known in the art. During the demethylation process to produce beta-conidendrol, it has been suggested that a racemization or inversion occurs probably at the carbon atom adjacent to the carbonyl group to produce both alphaand beta-conidendrol. These two compounds are considered to be optical isomers, differing only in spatial configuration, the two formulae being identical to that set forth above. However, they have differing physical properties, enabling separation of the two by such means as solvent extraction. Both compounds are commercially available.

We have found that the resistance of parafiin wax to oxidation can be materially increased, and the temperature to which it can be heated without breakdown can be substantially raised by addition to the wax of relatively small amounts of the conidendrols.

The conidendrols can be employed to advantage in paraffin Wax stabilization in amounts ranging from about 0.0001 to 0.1 per cent, by weight of the composition. A preferred range is from about 0.0005 to 0.01 per cent by weight of the composition. Mixtures of the conidendrols can also be employed.

The following illustrative examples permit further understanding of our invention and show the advantageous results obtained in wax compositions containing the conidendrols. For the purpose of the tests performed, a highly refined paraffin wax having a melting point of 122 F., as determined by ASTM method D87-42, was employed. The peroxide number, neutralization number and saponification number, referred to hereinafter, are all obtained by means of standard well known tests, and are indicative of the degree of oxidative breakdown of the parafiin wax subjected to oxidation.

EXAMPLE I A blend was prepared employing a 122 F., ASTM melting point, parafiin wax and 0.001 per cent, by weight, of alpha-conidendrol. Three hundred grams of the blend were placed in a glass oxidation cell suspended in an oil bath maintained at 240 F. Preheated dry air at a temperature substantially the same as that of the wax was passed upwardly through the molten wax at a controlled minimum rate of 1.6 cubic feet per hour. Once every 24 hours samples were withdrawn and the oxidation stability of the wax was measured by analyzing for peroxides,- acidity and saponifiable material by methods well known in the art. The odor also was noted.

Table I shows the results obtained along with data on the uninhibited wax control subjected to the same test conditions.

Table I Peroxide Neutralization Saponification Number, Number, Number, moles Ozl'kg. wax mg. KOH/gm.wax mg. KOH/gm. wax Days Oxidlzed Control Control Control Conplus 0011- plus Gonplus trol 0.001% trol 0.001%

Additive Additive It is readily seen that without the alpha-conidendrol additive of our invention all three measures of oxidative deterioration, viz., the peroxide number, the neutralization number and saponification number, increased rapidly with time, whereas values for the sample which contained the anti-oxidant showed no change even after seven days. The initial rise and subsequent drop in peroxide value for the uninhibited wax control is typical of wax oxidation.

The uninhibited wax developed a strong oxidized odor after one day of the test, but the inhibited sample did not develop such an odor for the full seven days of the run.

EXAMPLE II Another blend was prepared with 122 F., ASTM melting point, paraffin wax and 0.001 per cent, by weight, of beta-conidendrol. This composition was subjected to the oxidation test at 240 F., as described in Example I, and the odor was periodically noted. The composition did not develop an oxidized odor until after four days of oxidation, whereas the lminhibited control wax developed an odor insone day under the same conditions.

The above specific examples clearly demonstrate the efficacy, as paraffin wax anti-oxidants, of alphaand betaconidendrol. The complete lack of change in peroxide, neutralization and saponification numbers for the period of the test on alpha-conidendrol, coupled with the lack of odor formation after subjection of paraffin waxes inhibited with each compound to severe oxidative environment, indicate beyond any doubt that alphaand beta- ,conide'ndrol are remarkably effective paraffin wax antioxidants. Furthermore, the anti-oxidants are not only effective for inhibiting oxidation of parafiin wax in the hot liquefied condition, but since the anti-oxidant is retained by the wax in the finished wax treated product, the anti-oxidant continues thereafter to perform its desired function and aids in preventing subsequent deterioration of the paraflin wax due to adverse conditions of heat, air and the like.

The potency as paraffin wax anti-oxidants of the conidendrols permits of the employment of hot baths containing the inhibited parafiin wax compositions of this invention. In employing such baths, it is not necessary to use a paratfin wax already containing the antioxidant, but the anti-oxidant can be added in suitable amount to the molten paraffin wax in the bath in order to prevent the oxidative deterioration thereof.

Since the conidendrols can be employed so elfectively in relatively small amounts, they do not affect the odor and taste of the paraflin wax with which they are incorporated, and similarly, none of the desirable physical properties of the wax, such as melting point and tensile strength, are adversely affected.

As will be understood by those skilled in the art, the stabilized paraffin wax compositions of our invention may contain other additives and ingredients blended therewith to improve other characteristics, such as tensile strength, sealing strength, etc., of the composition.

While our invention has been described above with reference to certain specific examples and embodiments, it will be understood that the invention is not limited by such examples or embodiments, but that resort may be had to such modifications and variations as fall within the spirit of the invention and the scope of the appended c arms.

What we claim is:

1. An improved wax composition comprising a major amount of a paraflin wax and a minor amount, sufiicient to inhibit oxidative deterioration, of alpha-conidendrol substantially free from beta-conidendrol.

An improved wax composition comprising a major amount of a paraifin wax and from about 0.0005 to 0.01 per cent, by weight, of alpha-conidendrol substantially free from beta-conidendrol.

3. The method of preventing decomposition of a molten paraffin wax bath which comprises maintaining therein, in an amount suflicient to inhibit oxidative deterioration, alpllta-conidendrol substantially free from beta-conidendro 4. The method of preventing decomposition of a molten paraflin wax bath which comprises maintaining therein from about 0.0005 to 0.01 per cent, by weight, of alpha conidendrol substantially free from beta-conidendrol.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,116,220 Shoemaker May 3, 1938 2,564,106 Gribbins et al Aug. 14, 1951 OTHER REFERENCES Journal of American Oil Chemists Society, vol. 24, pages 340-343; by Fisher et al.; October 1947. 

1. AN IMPROVED WAX COMPOSITION COMPRISING A MAJOR AMOUNT OF A PARAFFIN WAX AND A MINOR AMOUNT, SUFFICIENT TO INHIBIT OXIDATIVE DETERIORATION, OF ALPHA-CONIDENDROL SUBSTANTIALLY FREE FROM BETA-CONIDENDROL. 